Mesophase pitches were prepared by segmental hydrogenation/thermal condensation using Shenhua coal liquefaction residue refined pitch (CLP) as raw material, and the effects of tetralin (THN) addition (5 ∼ 15 wt%) and hydrogenation temperature (350 ∼ 450 °C) on the structure and properties of the resulting products were investigated. The results showed that the H/C atomic ratio of the hydrogenated pitch (HP-12.5%) reached 0.64 at the temperature of 400 °C and THN addition of 12.5 %, and the content of the generated mesophase reached 76.0 % after heat treatment, which increased by 33.5 % compared with the mesophase content without hydrogenation. And the optical texture of the mesophase was improved from mosaic type to coarse fiber type and coarse flake type. The structures of the hydrogenated pitches were characterized by 1H NMR and FT-IR, which showed that the addition of THN increased the alkyl groups of the hydrogenated pitch molecules and resulted in more α- structures. The X-ray diffraction results showed a better orientation arrangement of pitch aromatic planar molecules due to enhanced fluidity of pitches caused by the increased alkyl structure after the addition of THN.